CN102510871B - Oxidant/dopant solution for conductive polymer production, a conductive polymer and a solid electrolyte capacitor - Google Patents

Abstract

The present invention provides an oxidizing agent and dopant solution suitable for producing conductive polymers. When the conductive polymers are used as solid electrolytes, they can provide high breakdown voltage, excellent voltage resistance and little leakage failure. A solid electrolytic capacitor; In addition, a conductive polymer and a solid electrolytic capacitor using the oxidizing agent and dopant solution and having the above-mentioned properties are provided. A compound having a glycidyl group or a ring-opened compound thereof is added to an oxidizing agent and dopant solution for producing a conductive polymer containing organic iron sulfonate as an oxidizing agent and dopant and an alcohol having 1 to 4 carbon atoms . In addition, it is preferable to further add a polyhydric alcohol. Then, thiophene or its derivatives are oxidatively polymerized using these oxidizing agent and dopant solutions to produce a conductive polymer, and the conductive polymer is used as a solid electrolyte to form a solid electrolytic capacitor.

Description

Oxidant and dopant solutions for the production of conductive polymers, conductive polymers, and solid electrolytic capacitors

technical field

The present invention relates to an oxidizing agent and dopant solution for producing conductive polymers, a conductive polymer produced by oxidatively polymerizing thiophene or its derivatives using the solution, a solid electrolytic capacitor using the conductive polymer as a solid electrolyte, and the like Manufacturing method. the

Background technique

Conductive polymers can be used as solid electrolytes for solid electrolytic capacitors such as aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, and niobium solid electrolytic capacitors due to their high conductivity. the

As the conductive polymer in this application, conductive polymers obtained by oxidative polymerization (chemical oxidative polymerization) of thiophene or its derivatives are often used because of the balance between conductivity and heat resistance and high usefulness. (Patent Documents 1 to 2). the

As a dopant in the chemical oxidation polymerization of the above-mentioned thiophene or its derivatives, etc., an organic sulfonic acid is used, and a transition metal is used as an oxidizing agent. Among them, it is recognized that ferric iron is the most suitable, and ferric salt of organic sulfonic acid is usually used as It is used as an oxidizing agent and dopant in the chemical oxidation polymerization of thiophene or its derivatives. the

Moreover, when producing a solid electrolytic capacitor using the conductive polymer as a solid electrolyte, for example, the capacitor element is immersed in a monomer solution, and after taking it out, the capacitor element is immersed in an oxidizing agent and dopant solution, and after taking it out, Polymerization; or immerse the capacitor element in the oxidant and dopant solution, take it out and immerse the capacitor element in the monomer solution, take it out and polymerize; or mix the oxidant and dopant and the monomer solution in the mixed solution prepared Immerse the capacitor element in the medium and take it out for polymerization. the

Yet, when making above-mentioned this solid electrolytic capacitor, so far, it has been reported that iron p-toluenesulfonate is used as oxidant and dopant concurrently. When thiophene or its derivatives are oxidatively polymerized, although ESR (equivalent series It is a solid electrolytic capacitor with low electrical resistance and large electrostatic capacity, but its withstand voltage (breakdown voltage) is low, so it cannot be used to manufacture high-voltage solid electrolytic capacitors (Patent Document 3). the

Patent Documents

Patent Document 1: Japanese Patent Laid-Open No. 2003-160647

Patent Document 2: Japanese Patent Laid-Open No. 2004-265927

Patent Document 3: Japanese Patent Laid-Open No. 2008-172277

Contents of the invention

The present invention is based on the above-mentioned problems, and its object is to provide a conductive polymer production oxidizing agent and dopant solution suitable for the production of conductive polymers. When the conductive polymer is used as a solid electrolyte, it can provide A solid electrolytic capacitor with low ESR, high capacitance while maintaining a large electrostatic capacity, and a high withstand voltage; also, a conductive polymer and a solid electrolytic capacitor using the oxidizing agent and dopant solution and having the above-mentioned properties are provided. the

The present invention achieves the above object by adding a compound having a glycidyl group or a ring-opened compound thereof to a solution of an oxidizing agent and dopant for producing a conductive polymer, and the present invention was completed based on this fact. the

That is, the present invention relates to an oxidizing agent and dopant solution for producing a conductive polymer containing an organic The solution of iron sulfonate and alcohol with 1 to 4 carbon atoms is characterized in that a compound having a glycidyl group or a ring-opening compound thereof is added. the

Also, the present invention relates to an oxidizing agent and dopant for conductive polymer production, wherein a polyhydric alcohol is added in addition to the above-mentioned compound having a glycidyl group or a ring-opened compound thereof. the

Also, the present invention relates to a conductive polymer characterized in that the conductive polymer is produced by oxidatively polymerizing thiophene or a derivative thereof using the above-mentioned oxidizing agent and dopant solution for producing a conductive polymer. the

Furthermore, the present invention relates to a solid electrolytic capacitor and a method for producing the same, characterized in that a conductive polymer produced by oxidative polymerization of thiophene or a derivative thereof is used as a solid electrolyte using the above-mentioned oxidizing agent and dopant solution for producing a conductive polymer use. the

The oxidizing agent and dopant solution for producing conductive polymers of the present invention (hereinafter, simply referred to as "oxidizing agent and dopant solution") is obtained by adding a compound having 1 to 4 glycidyl groups or a ring-opened compound thereof, and using the oxidizing agent As a concurrent dopant, thiophene or its derivatives are oxidatively polymerized to produce conductive polymers, and the resulting conductive polymers are used as solid electrolytes to provide low (small) ESR and maintain large ( High) electrostatic capacity, and solid electrolytic capacitors with high withstand voltage. the

In addition, when a solid electrolytic capacitor is produced by using a conductive polymer produced by oxidative polymerization of thiophene or its derivatives as a solid electrolyte using the oxidizing agent and dopant solution of the present invention, a solid electrolytic capacitor with less occurrence of leakage defects can be provided. the

Detailed ways

In the present invention, as the organic sulfonic acid of iron organic sulfonate forming the oxidizing agent and dopant solution, for example, benzenesulfonic acid or its derivatives, naphthalenesulfonic acid or its derivatives, anthraquinonesulfonic acid or its derivatives are suitably used. Such as aromatic sulfonic acid, and polymer sulfonic acid such as polystyrene sulfonic acid, sulfonated polyester, phenol sulfonic acid novolac resin, etc. the

As the benzenesulfonic acid derivatives in the above-mentioned benzenesulfonic acid or its derivatives, for example, toluenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid , methoxybenzenesulfonic acid, ethoxybenzenesulfonic acid, propoxybenzenesulfonic acid, butoxybenzenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, benzene disulfonic acid, etc., as naphthalenesulfonic acid or Naphthalenesulfonic acid derivatives in the derivatives include, for example, naphthalene disulfonic acid, naphthalene trisulfonic acid, methylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, etc., as Anthraquinonesulfonic acid derivatives in anthraquinonesulfonic acid or derivatives thereof include, for example, anthraquinonedisulfonic acid, anthraquinonetrisulfonic acid, and the like. As these aromatic sulfonic acids, toluenesulfonic acid, methoxybenzene Sulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, naphthalenetrisulfonic acid, etc., p-toluenesulfonic acid and methoxybenzenesulfonic acid are particularly preferred, and p-toluenesulfonic acid is especially preferred. the

In addition, the organic sulfonic acid iron is preferably an organic sulfonic acid having an organic sulfonic acid molar ratio of less than 1:3 with respect to the iron. This is because the reaction rate of the ferric organosulfonate can be slightly reduced by making the organosulfonic acid less than the 1:3 molar ratio relative to the iron relative to the iron The molar ratio of is preferably about 1:2, more preferably about 1:2.2, especially about 1:2.4, further preferably about 1:2.75. the

Alcohols with 1 to 4 carbon atoms are used to dissolve the organic iron sulfonate as the above-mentioned oxidizing agent and dopant to form a solution. As the alcohols with 1 to 4 carbon atoms, methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), butanol (butyl alcohol), etc., propanol or butanol may be linear or branched. the

Furthermore, as a compound having a glycidyl group, for example, a monoglycidyl compound represented by the following general formula (1), a diglycidyl compound represented by the general formula (2), a The indicated diglycidyl compounds, glycerol triglycidyl ether, diglyceryl tetraglycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, cresyl glycidyl ether, cyclohexanedi Methanol diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane triglycidyl ether, alcohol-soluble epoxy resin, alcohol-soluble polyglycerol polyglycidyl ether and their ring-opening compounds, etc. as a suitable substance. the

General formula (1):

( ^R1 in the formula is a hydroxyl group, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 7 carbon atoms)

General formula (2):

( ^R2 in the formula is an alkylene group with 2 to 6 carbon atoms)

General formula (3):

( ^R3 in the formula is an alkylene group with 2 to 4 carbon atoms, and n is 2 to 20)

In addition, the above-mentioned glycerol triglycidyl ether is represented by the following formula (4). the

Formula (4):

In addition, the above-mentioned diglycerol tetraglycidyl ether is represented by the following formula (5). the

Formula (5):

Then, the monoglycidyl compound represented by the above general formula (1), the diglycidyl compound represented by the general formula (2), the diglycidyl compound represented by the general formula (3), the triglyceride Glycidyl ether, diglyceryl tetraglycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, cresyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether Ring-opened compounds such as glyceryl ether and trimethylolpropane triglycidyl ether mean that the glycidyl group of these compounds having a glycidyl group is ring-opened as shown in the following formula (6) to form a diol. the

Formula (6):

The monoglycidyl compound represented by the general formula (1), the diglycidyl compound represented by the general formula (2), the diglycidyl compound represented by the general formula (3), glycerol triglycidyl ether, Diglycerol tetraglycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, cresyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether , trimethylolpropane triglycidyl ether, etc. are compounds with 1 to 4 glycidyl groups. In the present invention, these compounds with 1 to 4 glycidyl groups and their ring-opening compounds are suitable for use; but as Compounds or ring-opening compounds having glycidyl groups in the present invention, in addition to the above-mentioned compounds having 1 to 4 glycidyl groups or ring-opening compounds thereof, alcohol-soluble epoxy resins or ring-opening compounds thereof and alcohol-soluble epoxy resins can also be used. Polyglycerol polyglycidyl ether or its ring-opened compound, etc. In addition, as the above-mentioned alcohol-soluble epoxy resin, for example, a product sold under the trade name "Wootall BC-3010" from DIC Corporation can be used suitably. In addition, as the alcohol-soluble polyglycerol polyglycidyl ether, for example, a product sold under the trade name "SR-4GLS" by Sakamoto Pharmaceutical Co., Ltd. is suitably used. As shown in the above formula (6), the ring-opened compounds of these alcohol-soluble epoxy resins and alcohol-soluble polyglycerol polyglycidyl ethers are also ring-opened diols formed by the glycidyl groups they have. the

In addition, the ring-opened compound of the above-mentioned compound having a glycidyl group may be partially ring-opened in the case of a compound having two or more glycidyl groups, and not all glycidyl groups are necessarily ring-opened. the

Here, as specific examples of the monoglycidyl compound represented by the above formula (1) or its ring-opened compound, for example, glycidyl alcohol (that is, glycidol), methyl glycidyl ether, ethyl Glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, butylene oxide (that is, glycidyl methane), pentylene oxide (that is, glycidyl ethane), hexylene oxide alkanes (i.e., glycidylpropane), epoxyheptanes (i.e., glycidylbutanes), epoxyoctanes (i.e., glycidylpentanes), epoxycyclohexenes, etc., particularly preferred cyclohexene oxides Oxypropanol, butyl glycidyl ether, butylene oxide, etc. The monoglycidyl compound represented by the general formula (1) is a compound having one glycidyl group. Although the aforementioned glycidyl methacrylate, phenyl glycidyl ether, cresyl glycidyl ether, etc. are not included in Within the scope of the monoglycidyl compound represented by the general formula (1), but the same as the monoglycidyl compound represented by the general formula (1), it is a compound having one glycidyl group, and these glycidyl methacrylate Esters, phenyl glycidyl ethers, and cresyl glycidyl ethers are included in the range of substances particularly suitable for use in the present invention. the

In addition, examples of the diglycidyl compound represented by the general formula (2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, and pentanediol diglycidyl ether. , hexanediol diglycidyl ether, glycerin diglycidyl ether, etc., particularly preferably ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and the like. The diglycidyl compound represented by the general formula (2) is a compound having two glycidyl groups, although the aforementioned cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, etc. are not included in the general formula The diglycidyl compound represented by (2) is within the range, but it is a compound having two glycidyl groups similarly to the diglycidyl compound represented by the general formula (2). the

Then, examples of the diglycidyl compound represented by the general formula (3) include diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. Glyceryl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly 1,4-butylene glycol diglycidyl ether, etc., particularly preferably polyethylene glycol diglycidyl ether, poly 1,4-butyl Diol diglycidyl ether. the

The above-mentioned compound having a glycidyl group or its ring-opened compound may be used alone, or two or more thereof may be used in combination. the

The above-mentioned compounds having a glycidyl group or their ring-opened compounds are high-boiling compounds (for example, the boiling point of ethylene glycol diglycidyl ether is 112°C/0.6kPa), and they cannot be removed under normal drying, and may remain in the In the conductive polymer, even if it remains, it does not cause an increase in ESR or a decrease in capacitance as shown in Examples described later, and also does not cause a decrease in withstand voltage. the

The above-mentioned compound with glycidyl group or its ring-opening compound relative to the addition amount of organic sulfonate iron is preferably 2 to 40% on a mass basis (that is, with respect to 100 parts by mass of organic sulfonate iron, the compound with glycidyl group or its ring-opening compound is 2 to 40 parts by mass), when the added amount of the compound having a glycidyl group or its ring-opening compound is less than the above, it may not be able to fully exert the effect of reducing leakage and improving the withstand voltage; in addition , when the addition amount of the compound having glycidyl group or its ring-opening compound is more than the above, the increase of the effect caused by the increase of the addition amount is small, resulting in high cost, and it becomes unmixed, reducing the oxidant and Storage stability of dopant solutions. Furthermore, the added amount of the compound having a glycidyl group or its ring-opened compound relative to the organic iron sulfonate is within the above range, more preferably 5% or more, further preferably 10% or more and 36% or less on a mass basis. In particular, in order to more reliably exert the effect of improving the withstand voltage, the addition amount of the compound having a glycidyl group or its ring-opened compound relative to the organic sulfonate iron is preferably 10 to 40% by mass (that is, The compound having a glycidyl group or its ring-opened compound is 10 to 40 parts by mass), more preferably 14% or more, and more preferably 36% or less with respect to 100 parts by mass of organic iron sulfonate. the

In the oxidant and dopant solution to which the above-mentioned compound having a glycidyl group or its ring-opening compound is added, if a polyhydric alcohol is further added, the effect of improving the withstand voltage based on the addition of the compound having a glycidyl group can be further enhanced, And can further reduce ESR. the

As the polyhydric alcohol, those having 2 to 3 hydroxyl groups in aliphatic hydrocarbons having 2 to 10 carbon atoms are preferable, and specific examples of such a polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, amyl glycol, Glycol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, glycerin, etc., particularly preferably glycerin, ethylene glycol, propylene glycol, butanediol. the

If a small amount of polyhydric alcohol is added, the effect of adding the polyhydric alcohol will increase corresponding to the amount of addition. In order to show the effect of adding more clearly, it is preferable to make the amount of polyhydric alcohol added relative to the organic sulfonate, on a mass basis It is more than 4% (that is, relative to 100 mass parts of organic iron sulfonate, the addition of polyhydric alcohol is 4 mass parts); Therefore, the amount of polyhydric alcohol to be added is preferably 20% or less on a mass basis relative to the organic iron sulfonate. the

In addition, there is no restriction on the order of addition of the compound having a glycidyl group or its ring-opening compound and the polyhydric alcohol, both can be added at the same time, or one of them can be added first, and then the other can be added. In addition, A compound having a glycidyl group or a ring-opened compound thereof reacts with a polyhydric alcohol in advance and is added as a reactant. the

The concentration of the organic iron sulfonate in the oxidizing agent and dopant solution for the production of conductive polymers varies depending on the type of alcohol used to form the solution, and generally the higher the better, the range is preferably 25 to 60% by mass, and more preferably Preferably it is the range of 30-60 mass %. the

In the present invention, thiophene or a derivative thereof can be used as a monomer for producing a conductive polymer. As mentioned above, the conductive polymer obtained by polymerizing thiophene or its derivatives has a balanced conductivity and heat resistance, and it is easier to obtain a solid electrolytic capacitor having excellent capacitor properties than other monomers. the

Then, examples of thiophene derivatives in the thiophene or its derivatives include 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4 -Alkoxythiophene, 3,4-alkylthiophene, 3,4-alkoxythiophene, and alkylated ethylenedioxythiophene formed by modifying the above-mentioned 3,4-ethylenedioxythiophene with an alkyl group, etc. , the number of carbon atoms in the alkyl or alkoxy group is preferably 1-16, particularly preferably 1-4. the

The above-mentioned alkylated ethylenedioxythiophene formed by modifying 3,4-ethylenedioxythiophene with an alkyl group is carried out, then the above-mentioned 3,4-ethylenedioxythiophene and alkylated ethylenedioxythiophene Oxythiophene corresponds to a compound represented by the following general formula (7). the

Formula 7:

(wherein, R ⁴ is hydrogen or alkyl)

Moreover, the compound in which R ⁴ is hydrogen in the above-mentioned general formula (7) is 3,4-ethylenedioxythiophene, and if represented by the IUPAC name, it is "2,3-dihydro-thieno[3,4- b][1,4]dioxin (2,3-Dihydro-thieno[3,4-b][1,4]dioxine)", compared with the name of IUPAC, the compound is more common name"3,4-Ethylenedioxythiophene" means, so in this specification, hereinafter, the "2,3-dihydro-thieno[3,4-b][1,4]dioxin" is represented by "3,4-ethylenedioxythiophene" means. And, when R in the above general formula (7) is an alkyl group, as the alkyl group is an alkyl group with 1 to 4 carbon atoms, that is, preferably a methyl group, ^an ethyl group, a propyl group, a butyl group, if Represented by their specific examples, the compound in which R in the general formula (7) is ^a methyl group, if represented by the IUPAC name, is "2-methyl-2,3-dihydro-thieno[3,4 -b] [1, 4] dioxin (2-Methyl-2, 3-dihydro-thieno [3, 4-b] [1, 4] dioxine)", in this specification, it will be simplified as "a Alkylated ethylenedioxythiophene" means. The compound in which R in the general formula (7) is ^ethyl is "2-ethyl-2,3-dihydro-thieno[3,4-b][1,4] if represented by the IUPAC name Dioxin (2-Ethyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine)", in this specification, it is simplified as "ethylated ethylenedioxythiophene "express. R in the general formula (7) is ^a compound of propyl, if represented by the IUPAC name, it is "2-propyl-2,3-dihydro-thieno[3,4-b][1,4] Dioxin (2-Propyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine)", in this specification, it is simplified as "propylated ethylenedioxythiophene "express. Then, the compound in which R in the general formula (7) is ^butyl , if represented by the IUPAC name, is "2-butyl-2,3-dihydro-thieno[3,4-b][1, 4] Dioxin (2-Butyl-2, 3-dihydro-thieno [3, 4-b] [1, 4] dioxine)", in this specification, it is simplified as "butylated ethylene di Oxythiophene" said. In addition, "2-alkyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin" is simplified as "alkylated ethylenedioxythiophene" in this specification "express. Then, among these alkylated ethylenedioxythiophenes, methylated ethylenedioxythiophene, ethylated ethylenedioxythiophene, propylated ethylenedioxythiophene, butylated ethylenedioxythiophene, and butylated ethylenedioxythiophene are preferred. ethylenedioxythiophene, particularly preferably ethylated ethylenedioxythiophene, propylated ethylenedioxythiophene.

3,4-Ethylenedioxythiophene (i.e., 2,3-dihydro-thieno[3,4-b][1,4]dioxin) is then preferably combined with alkylated ethylene Dioxythiophene (that is, 2-alkyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin) is used in combination, and the mixing ratio is 0.1 in molar ratio :1 to 1:0.1, more preferably 0.2:1 to 1:0.2, especially preferably 0.3:1 to 1:0.3. the

The use of the oxidant and dopant solution of the present invention to produce conductive polymers can be applied to the production of general conductive polymers and the production of conductive polymers in the manufacture of solid electrolytic capacitors. These two collectively referred to as "in-situ polymerization" "To make conductive polymers. the

Thiophene or its derivatives as monomers are liquid at room temperature, so they can be used directly during polymerization, or in order to carry out the polymerization reaction more smoothly, for example, methanol, ethanol, propanol, butanol, acetone, acetonitrile, etc. can be used and other organic solvents to dilute the monomer and use it as an organic solvent solution. the

In the case of producing general conductive polymers (the above-mentioned production of general conductive polymers refers not to the case of producing conductive polymers by "in-situ polymerization" when manufacturing solid electrolytic capacitors), Use the mixture formed by mixing the oxidant and dopant solution of the present invention and monomer thiophene or its derivatives (the mixing ratio is based on mass, preferably oxidant and dopant:monomer is 5:1～15:1 ), for example, at 5-95° C., oxidative polymerization is carried out for 1-72 hours. the

The oxidizing agent and dopant solution of the present invention is particularly suitable for the so-called "in-situ polymerization" of monomeric thiophene or its derivatives in the manufacture of solid electrolytic capacitors to produce conductive polymers. described in detail. the

In addition, solid electrolytic capacitors also include aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, niobium solid electrolytic capacitors, etc., and the aluminum solid electrolytic capacitors also include wound aluminum solid electrolytic capacitors and laminated aluminum solid electrolytic capacitors. The oxidant of the present invention Since the co-dopant solution is particularly suitable for development for the manufacture of wound-type aluminum solid electrolytic capacitors, it will be specifically described in detail. the

First, as a capacitor element of a wound-type aluminum solid electrolytic capacitor, a capacitor element is used in which the surface of an aluminum foil is etched and then chemically converted, and a lead terminal is attached to an anode on which a dielectric layer is formed. Lead terminals are attached to cathodes formed of aluminum foil, and these anodes and cathodes with lead terminals are wound through separators to manufacture capacitor elements. the

Then, a wound aluminum solid electrolytic capacitor is manufactured using the capacitor element described above, for example, as follows. the

That is, the above-mentioned capacitor element is immersed in the mixture of the oxidizing agent and dopant solution of the present invention and the monomer (thiophene or its derivatives), and after taking it out, the monomer is polymerized at room temperature or under heating to form a capacitor composed of thiophene or its derivatives. After the polymer of its derivatives is a solid electrolyte layer formed by the conductive polymer of the polymer skeleton, the capacitor element with the solid electrolyte layer is externally encapsulated with an external packaging material to manufacture a wound aluminum solid electrolytic capacitor. the

In addition, as described above, instead of immersing the capacitor element in the mixture of the oxidizing agent and dopant solution of the present invention and the monomer, the monomer (thiophene or its derivative) may be diluted with the aforementioned organic solvent such as methanol. Immerse the capacitor element in the monomer solution, take it out and dry it, immerse the capacitor element in the oxidizing agent and dopant solution of the present invention, polymerize the monomer at room temperature or under heating after taking it out; or impregnate the capacitor element in the present invention The oxidizing agent and dopant solution, after taking out, the capacitor element is immersed in the monomer, and after taking out, the monomer is polymerized at room temperature or under heating, and thereafter, a wound aluminum solid electrolytic capacitor is manufactured in the same manner as above. the

When manufacturing solid electrolytic capacitors other than the above-mentioned winding type aluminum solid electrolytic capacitors, such as laminated aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, and niobium solid electrolytic capacitors, as capacitor elements, valve metals such as aluminum, tantalum, and niobium are used. The anode formed of the porous material, and the element of the dielectric layer formed by the oxide coating film of these valve metals, this capacitor element is the same as the case of the above-mentioned wound type aluminum solid electrolytic capacitor, impregnated with the oxidant of the present invention. In the mixture of impurity solution and monomer, take it out and polymerize the monomer (thiophene or its derivatives) at room temperature or under heating; or immerse the capacitor element in the monomer solution, take it out and dry it, then immerse the capacitor element in In the oxidizing agent and dopant solution of the present invention, take it out at room temperature or under heating to polymerize the monomer; or immerse the capacitor element in the oxidizing agent and dopant solution of the present invention, and then immerse the capacitor element in the monomer after taking it out. After taking it out, the monomer is polymerized at room temperature or under heating, and the capacitor element is washed and dried. Then, repeating these steps, after forming a solid electrolyte layer made of conductive polymers, applying carbon paste and silver paste, drying, and external packaging, thereby manufacturing laminated aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, and niobium solid electrolytic capacitors. electrolytic capacitors, etc. the

"In situ polymerization" during the manufacture of the above-mentioned conductive polymers and the manufacture of solid electrolytic capacitors. The use ratio of the bulk solution is 2:1 to 8:1 in terms of mass ratio between the organic iron sulfonate and the monomer as the oxidizing agent and dopant, and the "in-situ polymerization" is carried out at 10 to 300°C for example at 1 to 180°C. minute. the

In addition, when manufacturing a solid electrolytic capacitor, when the capacitor element is immersed in the oxidizing agent and dopant solution of the present invention and the monomer mixture, usually, the oxidizing agent and dopant solution of the present invention is prepared in advance, and it is mixed with the monomer Mixture, also can not carry out this pre-preparation, but the alcoholic solution (alcoholic solution that carbon number is 1～4) of organic sulfonate iron and the compound or its ring-opening compound that have glycidyl group, and then according to need and Polyhydric alcohol, monomer are mixed, and in this mixing state, can exist the alcoholic solution of the organic sulfonate ferric that is equivalent to the oxygenant of the present invention and dopant solution concurrently and have glycidyl compound or its ring-opening compound, and then according to Polyols may also be present if desired. the

Example

Next, although an Example is given and this invention is demonstrated more concretely, this invention is not limited only to the content illustrated in these Examples. In addition, in the following examples, % at the time of expressing a density|concentration and an addition amount is a mass basis % unless the standard is marked. the

[Preparation of oxidant and dopant solution (1)]

Embodiment 1～30 and comparative example 1～3

In Examples 1-30 and Comparative Examples 1-3, iron p-toluenesulfonate was used as an organic iron sulfonate forming an oxidizing agent and a dopant, and as a compound having a glycidyl group (hereinafter referred to simply as "glycidol") base compound"), in Examples 1 to 10, polyethylene glycol diglycidyl ether belonging to the diglycidyl compound represented by general formula (3) [SR-8EGS (trade name ), n in the general formula (3) is the middle value 8] of this polyethylene glycol diglycidyl ether, use respectively in embodiment 11,12,13 belong to the diglycidol shown in general formula (2) Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and butanediol diglycidyl ether of the base compound are respectively used in embodiments 14, 15, 16, 17, and 18 and belong to the formula (3). Diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether of the diglycidyl compounds shown Ether [SR-4PG (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd., n in the general formula (3) is the median value 7 of the polypropylene glycol diglycidyl ether], in Example 19, glycerol triglycidyl Base ether, use diglycerol tetraglycidyl ether in embodiment 20, in embodiment 21, use the glycidyl alcohol that belongs to the monoglycidyl compound shown in general formula (1), in embodiment 22,23 In Example 24, the monoglycidyl compound represented by the general formula (1) was used to use butylene oxide and octyl oxide, which belong to the ring-opening compound of the monoglycidyl compound represented by the general formula (1). The butyl glycidyl ether of the glyceryl compound uses glycidyl methacrylate, phenyl glycidyl ether, and cresyl glycidyl ether with one glycidyl group respectively in Examples 25 to 27. In Example 28, hexanediol diglycidyl ether belonging to the diglycidyl compound represented by the general formula (2) was used, and in Example 29, a diglycidyl compound belonging to the general formula (3) was used Poly 1,4-butanediol glycidyl ether, in Example 30, using the reactant of glycidyl methacrylate and butanediol prepared in Preparation Example 1 shown below; as polyhydric alcohol, In embodiment 1～6, embodiment 8, comparative example 2～3, use glycerol (glycerin), in embodiment 9, embodiment 11～20 and embodiment 25～30, use butanediol, in In Example 10 and Examples 21 to 24, hexanediol was used to prepare the oxidizing agent and dopant solution as follows. Among them, the type of glycidyl compound, its addition amount, its addition ratio relative to iron p-toluenesulfonate, the type of polyol, its addition amount, and its addition ratio relative to p-toluenesulfonate iron are listed in Table 1- In the relationship shown in Table 2, in the preparation method (1) of the oxidizing agent and dopant solution shown below, the type of glycidyl compound is represented by X, and the added amount of glycidyl compound is represented by A (g) Indicates that its addition ratio relative to iron p-toluenesulfonate is represented by B (%), the type of polyol is represented by Y, the amount of polyol added is represented by C (g), and its addition to iron p-toluenesulfonate The ratio is represented by D (%), and the amount of butanol added is represented by E (g). In addition, in the examples, there is an example (Example 7) in which only a diglycidyl compound is added and no polyhydric alcohol is added. In addition, in the comparative example, either a diglycidyl compound or a polyhydric alcohol is not added. Examples of species and examples of adding only polyols, etc. the

The preparation of the reactant of preparation example 1 glycidyl methacrylate and butanediol

284.3g (2.00mol) of glycidyl methacrylate, 90.1g (1.00mol) of butanediol and 1.0g of p-toluenesulfonic acid monohydrate were added to the reaction vessel, and the reaction vessel was kept at 80°C while stirring for 12 Hour. The reaction liquid was cooled to room temperature to obtain 375 g of a reaction product of glycidyl methacrylate and butanediol as a product. In addition, when the reactant of this glycidyl methacrylate and butanediol is shown in a table|surface, it shows with "production example 1" for simplicity. the

[The preparation method (1) of oxidant and dopant solution]

A 40% butanol solution of iron p-toluenesulfonate (the molar ratio of iron and p-toluenesulfonic acid: 1:2.74) manufactured by Teika Co., Ltd. was concentrated by distillation. The dry solids content was 67.2%. Add Ag glycidyl compound X, Cg polyol Y, and Eg butanol to 100 g of the above solution, and heat at 60° C. for 1 hour, then use a glass filter-GF75 manufactured by Advantec Toyo Co., Ltd. (GF75 is a product number, Hereinafter referred to as company name representation) filtration, this filtrate forms respectively the oxidizing agent solution of embodiment 1～30 and comparative example 1～3 concurrently dopant. The calculated solid content concentration of this solution was 43.0%. In addition, in Table 1 or Table 2, the addition ratio B% of glycidyl compound X to iron p-toluenesulfonate in these oxidizing agent and dopant solutions, the addition ratio of polyol Y to iron p-toluenesulfonate D% also corresponds to these Examples and Comparative Examples, respectively. Wherein, in Tables 1 to 2, glycidyl compounds and polyhydric alcohols are represented by the following abbreviations due to spatial relations. In addition, the evaluation of the oxidizing agent and dopant solutions of Examples 1 to 30 and Comparative Examples 1 to 3, and the oxidizing agent and dopant solutions of Examples 31 to 32 and Comparative Examples 4 to 6 described later was carried out from The evaluation of the solid electrolytic capacitor in [Evaluation (1) of the solid electrolytic capacitor] to [Evaluation of the solid electrolytic capacitor (8)] was performed. the

Glycidyl compounds

PEG-DG: polyethylene glycol diglycidyl ether

EG-DG: Ethylene glycol diglycidyl ether

PG-DG: Propylene Glycol Diglycidyl Ether

BG-DG: Butanediol diglycidyl ether

DEG-DG: Diethylene glycol diglycidyl ether

DPG-DG: Dipropylene Glycol Diglycidyl Ether

TEG-DG: Triethylene glycol diglycidyl ether

TPG-DG: Tripropylene Glycol Diglycidyl Ether

PPG-DG: polypropylene glycol diglycidyl ether

GL-TrG: Glycerol Triglycidyl Ether

DGL-TtG: Diglycerol Tetraglycidyl Ether

EPPOL: glycidyl alcohol

EPBTN: butylene oxide

EPOTN: Epoxy octane

BU-GE: Butyl glycidyl ether

Meth-G: Glycidyl Methacrylate Ether

Ph-G: Phenyl glycidyl ether

Cr-G: cresyl glycidyl ether

HexG-DG: Hexylene Glycol Diglycidyl Ether

PMG-DG: poly 1,4-butanediol diglycidyl ether

Polyol

GLYOL: Glycerin

BUDOL: butanediol

HEDOL: hexanediol

In addition, in Comparative Example 3, the polyethylene glycol 400 added instead of the glycidyl compound is simply represented by PEG400. the

[Table 1]

[Table 2]

[Preparation of oxidizing agent and dopant solution (2)]

Embodiment 31～32 and comparative example 4～6

In Examples 31 to 32 and Comparative Examples 4 to 6, iron methoxybenzenesulfonate was used as organic iron sulfonate; Polyethylene glycol diglycidyl ether (the same substance as in Example 1) of a diglycidyl compound. In Example 32, an epoxy resin belonging to a monoglycidyl compound represented by the general formula (1) is used. Propanol was used as the polyhydric alcohol in Examples 31-32 and Comparative Examples 5-6, and glycerin was used to prepare oxidizing agent and dopant solutions as follows. Wherein, the preparation of the oxidant and dopant solution using iron methoxybenzenesulfonate as the oxidant and dopant also involves the type of glycidyl compound, its addition amount, and its relative to iron methoxybenzenesulfonate The addition ratio of the polyhydric alcohol, the type of polyhydric alcohol, its addition amount, and its addition ratio to iron methoxybenzene sulfonate, with the relationship shown in Table 3, in the following [Preparation method of oxidizing agent and dopant solution In (2)], the type of glycidyl compound is also represented by X, the amount of glycidyl compound added is represented by A (g), and the ratio of its addition to iron methoxybenzenesulfonate is represented by B (%) Indicates that the type of polyol is represented by Y, the amount of polyol added is represented by C (g), the ratio of its addition to iron methoxybenzenesulfonate is represented by D (%), and the amount of ethanol added is represented by E (g )express. the

[The preparation method of oxidant and dopant solution (2)]

A 40% ethanol solution of iron methoxybenzenesulfonate (the molar ratio of iron and methoxybenzenesulfonic acid: 1:2.72) manufactured by Teika Co., Ltd. was concentrated by distillation. The dry solids content was 64.5%. Add Ag glycidyl compound X, Cg polyol Y, and Eg ethanol to 100 g of the above solution, heat at 60° C. for 1 hour, and filter with a glass filter GF75 manufactured by Advantec Toyo Co., Ltd. 31-32 and the oxidizing agent and dopant solutions of Comparative Examples 4-6. The calculated solid content concentration of this solution is 45.0%, the addition ratio of glycidyl compound X to iron methoxybenzenesulfonate is B%, and the addition ratio of polyol Y to iron methoxybenzenesulfonate is D%. The aforementioned X, Y, A, B, C, D, and E are specifically shown in Table 3. Also in Table 3, polyethylene glycol diglycidyl ether is abbreviated as "PEG-DG", glycidol is abbreviated as "EPPOL", and glycerin is abbreviated as "GLYOL". the

[table 3]

[Evaluation of solid electrolytic capacitors (1)] 

In this [Evaluation of Solid Electrolytic Capacitor (1)], 3,4-ethylenedioxythiophene was used as a monomer, and the oxidizing agent and dopant solutions of Examples 1 to 30 prepared as described above were used, The winding-type aluminum solid electrolytic capacitors of Examples 33 to 62 with a set electrostatic capacity of 10 μF or more and a set ESR of 40 mΩ or less were produced, and they were produced by using the oxidizing agent and dopant solution of Comparative Examples 1 to 3 prepared above. The capacitor properties of the winding type aluminum solid electrolytic capacitors of Comparative Examples 7 to 9 were compared, and at the same time, the oxidizing agents of Examples 1 to 30 and Comparative Examples 1 to 3 used in the manufacture of these winding type aluminum solid electrolytic capacitors were evaluated. properties of the dopant solution. the

Embodiment 33～62 and comparative example 7～9

First, the state of manufacturing the wound type aluminum solid electrolytic capacitor of Example 33 using the oxidizing agent and dopant solution of Example 1 is shown. the

Etch the surface of the aluminum foil, dip the etched aluminum foil into a 12% ammonia solution, apply a voltage of 80V to the aluminum foil in the ammonia solution, form a dielectric layer on the surface of the aluminum foil as an anode, and install on the anode In addition, lead terminals are attached to cathodes formed of aluminum foil, and these anodes and cathodes with lead terminals are wound with separators to manufacture winding-type aluminum with a set capacitance of 10μF or more and a set ESR of 40mΩ or less. Capacitor elements for the manufacture of solid electrolytic capacitors. the

The above-mentioned capacitor element was immersed in a monomer solution prepared by adding 80 ml of methanol to 20 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Co., Ltd.), taken out, and dried at 50° C. for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100 ml of the oxidizing agent and dopant solution of Example 1, and after taking it out, it was heated at 70° C. for 2 hours, and then at 180° C. for 1 hour, so that 3,4-ethylene as a monomer 3,4-ethylenedioxythiophene is polymerized to form a solid electrolyte layer formed of a conductive polymer with a polymer of 3,4-ethylenedioxythiophene as a polymer skeleton. This was externally sealed with an external sealing material to manufacture a wound aluminum solid electrolytic capacitor of Example 33. the

Then, except that the oxidizing agent and dopant solution of Examples 2 to 30 and Comparative Examples 1 to 3 were used instead of the oxidizing agent and dopant solution of Example 1, and the oxidizing agent and dopant solution of Example 1 were used. In the same manner, wound-type aluminum solid electrolytic capacitors using the oxidizing agent and dopant solutions were manufactured, and these were used as the wound-type aluminum solid electrolytic capacitors of Examples 34-62 and Comparative Examples 7-9. the

For the winding-type aluminum solid electrolytic capacitors of Examples 33-62 and Comparative Examples 7-9 manufactured as above, the ESR was measured at 100 kHz at 25°C using an LCR meter (4284A) manufactured by HEWLETT PACKARD, and at 120 Hz The electrostatic capacitance was measured under the condition of 25° C., and the breakdown voltage was measured at a rate of 1 V/min using PRk650-2.5 manufactured by Matsudaka Pressiyo Corporation. The results are shown in Tables 4 to 5. These measurements were carried out on 50 samples of each type. The ESR values and capacitance values shown in Table 4 and Table 5 are the average values of these 50 samples, and the values indicated by the second decimal point are rounded off. The breakdown voltage is the value expressed below the rounded decimal point. In addition, the oxidizing agent and dopant solution used is represented by an example number and a comparative example number. the

[Table 4]

[table 5]

As shown in Tables 4 to 5, the winding type aluminum solid electrolytic capacitors of Examples 33 to 62 and the winding type aluminum solid electrolytic capacitors of Comparative Examples 7 to 9 all have a capacitance of about 11 μF, which satisfies the set capacitance. 10μF or more, the ESR is about 30mΩ, which satisfies the set ESR of 40mΩ or less, but the breakdown voltage of the wound aluminum solid electrolytic capacitors of Comparative Examples 7-9 is 21-22V. In contrast, Examples 33- The breakdown voltage of the winding type aluminum solid electrolytic capacitor of 62 is about 40V, and the winding type aluminum solid electrolytic capacitors of Examples 33 to 62 are about twice as high as the winding type aluminum solid electrolytic capacitors of Comparative Examples 7 to 9 Breakdown voltage, excellent voltage resistance. the

That is, the wound-type aluminum solid electrolytic capacitor of Example 39 manufactured using the oxidizing agent and dopant solution of Example 7 to which only a glycidyl compound was added satisfies the specified capacitance and ESR, and the breakdown voltage It is 41V, which shows that the wound-type aluminum solid electrolytic capacitors of Comparative Examples 7 to 9 have a breakdown voltage nearly twice as high, and the withstand voltage is excellent; in addition, in addition to the glycidyl compound, an example in which a polyhydric alcohol is added 1-6. The wound-type aluminum solid electrolytic capacitors of Examples 33-38 and Examples 40-62 manufactured by the oxidizing agent and dopant solution of Examples 8-30 are more satisfied with the set electrostatic capacity and set ESR. , compared with the winding type aluminum solid electrolytic capacitor of Example 39 above, it has a higher breakdown voltage and better withstand voltage, and at the same time, the ESR is also lower than that of the winding type aluminum solid electrolytic capacitor of Example 39. In In this respect, improvement in properties can be confirmed. the

In contrast, the oxidizing agent and dopant solution of Comparative Example 1 in which no glycidyl compound and polyol was added was used; the oxidizing agent and dopant solution of Comparative Example 2 was used in which polyhydric alcohol was added and no glycidyl compound was added. Solution: Winding type aluminum solid electrolytic capacitors of Comparative Examples 7 to 9 manufactured using the oxidizing agent and dopant solution of Comparative Example 3 in which polyethylene glycol 400 (PEG400) was added and the glycidyl compound was changed to add polyhydric alcohol , although the set electrostatic capacity and set ESR are satisfied, the breakdown voltage is low, and the withstand voltage is worse than that of the embodiment. the

Then, from the results, it can be known that the oxidizing agent and dopant solutions of Examples 1-30 used in the manufacture of wound-type aluminum solid electrolytic capacitors of Examples 33-62 are different from the wound-type aluminum solid electrolytic capacitors of Comparative Examples 7-9. Compared with the oxidizing agent and dopant solutions of Comparative Examples 1 to 3 used in the production of capacitors, the properties as oxidizing agent and dopant solutions for the production of conductive polymers are superior, and it can be seen that the oxidizing agent and dopant solutions of Examples 1 to 30 are The oxidant and dopant solution is excellent in the properties of a conductive polymer produced by oxidative polymerization of 3,4-ethoxydioxythiophene. the

[Evaluation of solid electrolytic capacitors (2)] 

In this [Evaluation of Solid Electrolytic Capacitor (2)], 3,4-ethylenedioxythiophene was used as a monomer, and Examples 31 to 31 were used in which iron methoxybenzenesulfonate was used as an oxidant and dopant. 32 oxidizing agent and dopant solution, carry out oxidative polymerization to manufacture winding-type aluminum solid electrolytic capacitors of Examples 63-64 with a set electrostatic capacitance of 10 μF or more and a set ESR of 40 mΩ or less, and use them and the above-mentioned prepared The properties of the coiled aluminum solid electrolytic capacitors of Comparative Examples 10 to 12 manufactured by using the oxidant and dopant solutions of Comparative Examples 4 to 6 were compared, and at the same time, the implementation of these coiled aluminum solid electrolytic capacitors was evaluated. Properties of the oxidizing agent and dopant solutions of Examples 31-32 and Comparative Examples 4-6. the

Embodiment 63～64 and comparative example 10～12

First, the state of manufacturing the wound aluminum solid electrolytic capacitor of Example 63 using the oxidizing agent and dopant solution of Example 31 is shown below. the

The same capacitor element as used in Example 33 above was immersed in a monomer solution prepared by adding 80 ml of methanol to 20 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Co.), and dried at 50°C after taking it out. 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100 ml of the oxidizing agent and dopant solution of Example 25, and after taking it out, it was heated at 70°C for 2 hours, and at 180°C for 1 hour, so that the monomer 3,4-ethylenedi Oxythiophene is polymerized to form a solid electrolyte layer made of a conductive polymer having a polymer of 3,4-ethylenedioxythiophene as a polymer skeleton. This was externally encapsulated with an external sealing material to manufacture a wound aluminum solid electrolytic capacitor of Example 63. the

Then, except that the oxidizing agent and dopant solution of Example 32 and Comparative Examples 4 to 6 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 31, it was the same as the case of using the oxidizing agent and dopant solution of the above-mentioned Example 31. In this way, wound-type aluminum solid electrolytic capacitors were produced using various oxidizing agent and dopant solutions, and these were used as wound-type aluminum solid electrolytic capacitors of Example 64 and Comparative Examples 10-12. the

The winding-type aluminum solid electrolytic capacitors of Examples 63 to 64 and Comparative Examples 10 to 11 produced as above were measured in the same manner as in Example 33, and the results are shown in Table 6. the

[Table 6]

As shown in Table 6, the wound-type aluminum solid electrolytic capacitors of Examples 63-64 and the wound-type aluminum solid electrolytic capacitors of Comparative Examples 10-12 all have a capacitance of about 11 μF, satisfying the set capacitance of 10 μF or more , ESR are all about 30μΩ, satisfying the set ESR of 40mΩ or less, but the breakdown voltage of the wound aluminum solid electrolytic capacitors of Examples 63-64 is as high as 48V. In contrast, the coils of Comparative Examples 10-12 The breakdown voltage of the wound type aluminum solid electrolytic capacitor was 24 to 25 V, which was only about half of that of the wound type aluminum solid electrolytic capacitor of Examples 63 to 64. the

That is, it can be seen that the wound-type aluminum solid electrolytic capacitors of Examples 63-64 satisfy the set electrostatic capacity and set ESR, and the breakdown voltage is as high as 48V, which is different from that of the wound-type aluminum solid electrolytic capacitors of Comparative Examples 10-12. Compared with capacitors, the withstand voltage is excellent, and the situation using iron methoxybenzenesulfonate as an oxidizing agent and a dopant also finds the same tendency as the situation using iron p-toluenesulfonate as an oxidizing agent and a dopant; Examples 31- Compared with the oxidizing agent and dopant solutions of Comparative Examples 4 to 6, the oxidizing agent and dopant solution of 32 has better properties as an oxidizing agent and dopant solution for the production of conductive polymers. The oxidizing agent and dopant solutions of Examples 31 to 32 were excellent in the properties of wire polymers produced by oxidatively polymerizing 3,4-ethylenedioxythiophene. the

[Evaluation of solid electrolytic capacitors (3)] to [Evaluation of solid electrolytic capacitors (8)] shown below use alkylated ethylenedioxythiophene as a monomer for the production of conductive polymers, so in Before the description of [Evaluation of Solid Electrolytic Capacitor (3)] to [Evaluation of Solid Electrolytic Capacitor (8)], a synthesis example for synthesizing alkylated dioxythiophene is shown. the

Synthesis Example 1 Synthesis of methylated ethylenedioxythiophene (that is, 2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin)

Through the subsequent steps 1-(1) to 1-(3), methylated ethylenedioxythiophene was synthesized. the

Synthesis of 1-(1)propane-1,2-diyl-bis(4-methylbenzenesulfonate)

Under ice cooling, add 7.86kg (40mol) toluenesulfonyl chloride and 7kg of 1,2-dichloroethane to the reaction vessel, stir the temperature in the vessel to 10°C, and drop 5.11kg (50mol) triethyl amine. the

While stirring the above mixture, while keeping the temperature in the container not exceeding 40°C, 1.55kg (20mol) of 1,2-propanediol was carefully added dropwise to the mixture in 60 minutes at the same time, and the temperature in the container was kept at 40°C. At the same time the mixture was stirred for 6 hours. the

Cool the liquid after the reaction to room temperature, add 4kg of water and stir, then let stand. The liquid after the reaction was divided into two layers, an aqueous phase and an organic phase, and the organic phase was concentrated to obtain a black-red oil. the

Under ice-cooling, 500 g of methanol was added to the reaction vessel for stirring, and the black-red oil obtained above was added dropwise therein while stirring, and the precipitated white solid was collected by filtration. The white solid was washed with a small amount of methanol and then dried to obtain 3.87 kg of propane-1,2-diyl-bis(4-methylbenzenesulfonate) as a product. the

Synthesis of 1-(2) 2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin-5,7-dicarboxylic acid

Add 508g (1.67mol) disodium-2,5-bis(alkoxycarbonyl)thiophene-3,4-dioxolate, 960g (2.5mol) propane- 1,2-diyl-bis(4-methylbenzenesulfonate), 46g (0.33mol) of potassium carbonate and 2.5kg of dimethylformamide, while keeping the temperature in the container at 120°C, the mixture was stirred for 4 hours . the

Concentrate the liquid after the completion of the reaction, add 3.7kg of 5% aqueous sodium bicarbonate solution to the remaining brown solid, stir at room temperature for 15 minutes, and filter the brown solid. The filtered brown solid and 2.47 kg of a 7% aqueous sodium hydroxide solution were added to a reaction container, and stirred for 2 hours while maintaining the temperature in the container at 80°C. the

Cool the container to room temperature so that the temperature in the container does not exceed 30°C, and at the same time carefully add 759g of 98% sulfuric acid dropwise to the liquid after the reaction, and stir for 2 hours while keeping the temperature in the container at 80°C . the

The inside of the container was cooled to room temperature while stirring, and the precipitated gray solid was collected by filtration. Then, the liquid after the reaction was cooled, and the gray solid was collected by filtration. These gray solids were washed with a small amount of water and dried to obtain 310 g of 2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin-5,7- Diformic acid. the

Synthesis of 1-(3)methylated ethylenedioxythiophene (2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin)

880g (3.6mol) of 2-methyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin-5,7-dicarboxylic acid obtained in the above 1-(2) In the reaction vessel, dissolve in 3kg polyethylene glycol 300 (manufactured by Hayashi Pure Pharmaceutical Industry Co., Ltd.), add 176g of copper oxide, and the mixture slowly heats up under an internal pressure of 20hpa for distillation. Add 400g of water in the main distillate of alcohol 300, stir and let stand. the

The two-layered solution was separated to obtain 345 g of the yellow transparent liquid in the lower layer, which was the product methylated ethylenedioxythiophene. the

Synthesis Example 2 Synthesis of ethylated ethylenedioxythiophene (that is, 2-ethyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin)

Except for using 1,2-butanediol instead of 1,2-propanediol, the same operation as in Synthesis Example 1 was carried out to obtain 130 g of ethylated ethylenedioxythiophene as a yellow transparent liquid. the

Synthesis Example 3 Synthesis of propylated ethylenedioxythiophene (that is, 2-propyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin)

Except for using 1,2-pentanediol instead of 1,2-propanediol, the same operation as in Synthesis Example 1 was carried out to obtain 180 g of propylated ethylenedioxythiophene as a yellow transparent liquid. the

Synthesis Example 4 Synthesis of butylated ethylenedioxythiophene (that is, 2-butyl-2,3-dihydro-thieno[3,4-b][1,4]dioxin)

Except for using 1,2-hexanediol instead of 1,2-propanediol, the same operation as in Synthesis Example 1 was carried out to obtain 100 g of butylated ethylenedioxythiophene as a yellow transparent liquid. the

[Evaluation of solid electrolytic capacitors (3)]

In this [Evaluation of Solid Electrolytic Capacitor (3)], a mixture of 3,4-ethylenedioxythiophene and methylated ethylenedioxythiophene was used as a monomer, and the samples of Examples 3, 4, and 7 were used. The oxidant and dopant solution were used to oxidize and polymerize it to manufacture a wound aluminum solid electrolytic capacitor, and evaluate its capacitor properties. the

Examples 65-67

First, the state of manufacturing the wound aluminum solid electrolytic capacitor of Example 65 using the oxidizing agent and dopant solution of Example 3 is shown below. In addition, the capacitor elements used in Examples 65 to 67 are the same as those used in Example 33, etc., and the set capacitance of the wound aluminum solid electrolytic capacitor is 10 μF or more, and the set ESR is 40 mΩ or less. the

That is, 80 ml of methanol was added to a mixed solution of 5 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Co., Ltd.) and 15 ml of methylated ethylenedioxythiophene synthesized in Synthesis Example 1. Immerse the capacitor element in the monomer solution, take it out and dry it at 50°C for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 3, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers and form a compound composed of 3,4 -The polymer of the mixture of ethylenedioxythiophene and methylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton, and it is externally encapsulated with an external packaging material to manufacture Example 65 Winding type aluminum solid electrolytic capacitors. the

Then, except that the oxidizing agent and dopant solution of Example 4 and Example 7 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 3, the situation of using the oxidizing agent and dopant solution of the above-mentioned Example 3 was the same , Fabricated wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions, respectively, and used them as Example 66 and Example 67 wound-type aluminum solid electrolytic capacitors. the

For the wound aluminum solid electrolytic capacitors of Examples 65 to 67 manufactured as described above, ESR, capacitance, and breakdown voltage were measured in the same manner as in Example 33, and the results are shown in Table 7. the

[Table 7]

As shown in Table 7, the electrostatic capacitance of the winding type aluminum solid electrolytic capacitors of Examples 65 to 67 is 11.7 to 11.8 μF, which meets the set capacitance of 10 μF or more; the ESR is 32.4 to 32.9 mΩ, which meets the setting of 40 mΩ or less. The ESR was determined; the breakdown voltage showed a high value of 48 to 54, and the voltage resistance was excellent. the

Then, the wound-type aluminum solid electrolytic capacitors of Examples 65 to 67 were compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 using the same oxidizing agent and dopant solution. -A mixture of ethylenedioxythiophene and methylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitors of Examples 65 to 67, and 3,4-ethylenedioxythiophene alone Compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 as a single body, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

That is, both the wound type aluminum solid electrolytic capacitor of Example 65 and the wound type aluminum solid electrolytic capacitor of Example 35 used the oxidizing agent-cum-dopant solution of Example 3, but 3,4-ethylene The wound-type aluminum solid electrolytic capacitor of Example 35 in which dioxythiophene is used as a monomer is shown in Table 4. The breakdown voltage is 46V, the electrostatic capacity is 11.5μF, and the ESR is 34.7mΩ, while using 3,4-ethylene A mixture of ethylenedioxythiophene and methylated ethylenedioxythiophene as a monomer, the winding type aluminum solid electrolytic capacitor of Example 65 is shown in Table 7, the breakdown voltage is 56V, the electrostatic capacity is 11.8μF, and the ESR It was 31.1 mΩ, and compared with the wound aluminum solid electrolytic capacitor of Example 35, the breakdown voltage was higher, the electrostatic capacity was larger, the ESR was lower, and the capacitor properties were more excellent. the

In addition, comparing the wound-type aluminum solid electrolytic capacitor of Example 66 and the wound-type aluminum solid electrolytic capacitor of Example 36 using the same oxidizing agent and dopant solution of Example 4, the 3,4-submerged solid electrolytic capacitor was also used. The wound type aluminum solid electrolytic capacitor of Example 66 in which a mixture of ethyldioxythiophene and methylated ethylenedioxythiophene was used as a monomer, and the capacitor using 3,4-ethylenedioxythiophene alone as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 36, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

Then, the wound-type aluminum solid electrolytic capacitor of Example 67 using the same oxidizing agent and dopant solution of Example 7 was compared with the wound-type aluminum solid electrolytic capacitor of Example 39, also using 3,4-substrate The wound-type aluminum solid electrolytic capacitor of Example 67 in which a mixture of ethyldioxythiophene and methylated ethylenedioxythiophene was used as a monomer, and the capacitor using 3,4-ethylenedioxythiophene alone as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 39, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

[Evaluation of solid electrolytic capacitors (4)]

In this [Evaluation of Solid Electrolytic Capacitor (4)], a mixture of 3,4-ethylenedioxythiophene and ethylated ethylenedioxythiophene was used as a monomer, and the samples of Examples 3, 4, and 7 were used. The oxidant and dopant solution were used to oxidize and polymerize it to manufacture a wound aluminum solid electrolytic capacitor, and evaluate its capacitor properties. the

Examples 68-70

First, the state of manufacturing the wound aluminum solid electrolytic capacitor of Example 68 using the oxidizing agent and dopant solution of Example 3 is shown below. Note that the capacitor elements used in Examples 68 to 70 are the same as those used in Example 33 and the like, and the wound-type aluminum solid electrolytic capacitor has a set capacitance of 10 μF or more and a set ESR of 40 mΩ or less. the

That is, 80 ml of methanol was added to a mixed solution of 10 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Corporation) and 10 ml of ethylated ethylenedioxythiophene synthesized in Synthesis Example 2. Immerse the capacitor element in the monomer solution, take it out and dry it at 50°C for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 3, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers and form a compound composed of 3,4 -The polymer of the mixture of ethylenedioxythiophene and ethylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton, and it is externally encapsulated with an external packaging material to manufacture Example 68 Winding type aluminum solid electrolytic capacitors. the

Then, except that the oxidizing agent and dopant solution of Example 4 and Example 7 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 3, as in the case of using the oxidizing agent and dopant solution of the above-mentioned Example 3, Wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions were manufactured, and these were used as Example 69 and Example 70 wound-type aluminum solid electrolytic capacitors. the

For the wound aluminum solid electrolytic capacitors of Examples 68 to 70 manufactured as described above, ESR, electrostatic capacitance, and breakdown voltage were measured in the same manner as in Example 33, and the results are shown in Table 8. the

[Table 8]

As shown in Table 8, the electrostatic capacitance of the wound aluminum solid electrolytic capacitors of Examples 68 to 70 is 11.8 μF, satisfying the set electrostatic capacity of 10 μF or more; the ESR is 31.1 to 31.8 mΩ, satisfying the set ESR of 40 mΩ or less ; The breakdown voltage showed a high value of 49 to 56V, and the voltage resistance was excellent. the

Then, the wound-type aluminum solid electrolytic capacitors of Examples 68 to 70 were compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 using the same oxidizing agent and dopant solution. -A mixture of ethylenedioxythiophene and ethylated ethylenedioxythiophene as a monomer for the wound-type aluminum solid electrolytic capacitors of Examples 68 to 70, and 3,4-ethylenedioxythiophene alone Compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 as a single body, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

That is, both the wound type aluminum solid electrolytic capacitor of Example 68 and the wound type aluminum solid electrolytic capacitor of Example 35 used the oxidizing agent-cum-dopant solution of Example 3, but 3,4-ethylene The wound-type aluminum solid electrolytic capacitor of Example 35 in which dioxythiophene is used as a monomer is shown in Table 4. The breakdown voltage is 46V, the electrostatic capacity is 11.5μF, and the ESR is 34.7mΩ, while using 3,4-ethylene A mixture of ethylenedioxythiophene and ethylated ethylenedioxythiophene as a monomer, the winding type aluminum solid electrolytic capacitor of Example 68 is shown in Table 8, the breakdown voltage is 56V, the electrostatic capacity is 11.8μF, and the ESR It was 31.1 mΩ, and compared with the wound aluminum solid electrolytic capacitor of Example 35, the breakdown voltage was higher, the electrostatic capacity was larger, the ESR was lower, and the capacitor properties were more excellent. the

In addition, comparing the wound-type aluminum solid electrolytic capacitor of Example 69 and the wound-type aluminum solid electrolytic capacitor of Example 36 using the same oxidizing agent and dopant solution of Example 4, the 3,4-submerged solid electrolytic capacitor was also used. The wound type aluminum solid electrolytic capacitor of Example 69 in which a mixture of ethyldioxythiophene and ethylated ethylenedioxythiophene was used as a monomer, and 3,4-ethylenedioxythiophene alone was used as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 36, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

Then, the wound-type aluminum solid electrolytic capacitor of Example 70 using the same oxidizing agent-cum-dopant solution of Example 7 was compared with the wound-type aluminum solid electrolytic capacitor of Example 39, also using 3,4-substrate A mixture of ethyldioxythiophene and ethylated ethylenedioxythiophene as a monomer of the winding type aluminum solid electrolytic capacitor of Example 70, and a single use of 3,4-ethylenedioxythiophene as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 39, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

[Evaluation of solid electrolytic capacitors (5)] 

In this [Evaluation of Solid Electrolytic Capacitor (5)], a mixture of 3,4-ethylenedioxythiophene and propylated ethylenedioxythiophene was used as a monomer, and the samples of Examples 3, 4, and 7 were used. The oxidant and dopant solution were used to oxidize and polymerize it to manufacture a wound aluminum solid electrolytic capacitor, and evaluate its capacitor properties. the

Examples 71-73

First, the state of manufacturing the wound-type aluminum solid electrolytic capacitor of Example 71 using the oxidizing agent and dopant solution of Example 3 is shown below. The capacitor elements used in Examples 71 to 73 are also the same as those used in Example 33, and the wound-type aluminum solid electrolytic capacitor has a set capacitance of 10 μF or more and a set ESR of 40 mΩ or less. the

That is, 80 ml of methanol was added to a mixed solution of 13 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Co., Ltd.) and 7 ml of propylated ethylenedioxythiophene synthesized in Synthesis Example 3. Immerse the capacitor element in the monomer solution, take it out and dry it at 50°C for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 3, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers and form a compound composed of 3,4 -The polymer of the mixture of ethylenedioxythiophene and propylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton, which is externally encapsulated with an external packaging material, and the manufacturing example 71 winding type aluminum solid electrolytic capacitors. the

Then, except that the oxidizing agent and dopant solution of Example 4 and Example 7 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 3, as in the case of using the oxidizing agent and dopant solution of the above-mentioned Example 3, Wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions were manufactured, and these were used as Example 72 and Example 73 wound-type aluminum solid electrolytic capacitors. the

For the wound aluminum solid electrolytic capacitors of Examples 71 to 73 manufactured as described above, ESR, capacitance, and breakdown voltage were measured in the same manner as in Example 33, and the results are shown in Table 9. the

[Table 9]

As shown in Table 9, the electrostatic capacitance of the wound aluminum solid electrolytic capacitors of Examples 71 to 73 is 11.7 to 11.8 μF, satisfying the set capacitance of 10 μF or more; the ESR is 31.2 to 31.9 mΩ, meeting the setting of 40 mΩ or less The ESR was fixed; the breakdown voltage showed a high value of 48 to 55V, and the voltage resistance was excellent. the

Then, the wound-type aluminum solid electrolytic capacitors of Examples 71 to 73 were compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 using the same oxidizing agent and dopant solution. -A mixture of ethylenedioxythiophene and propylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitors of Examples 71 to 73, and 3,4-ethylenedioxythiophene alone Compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 as a single body, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

That is, both the wound type aluminum solid electrolytic capacitor of Example 71 and the wound type aluminum solid electrolytic capacitor of Example 35 used the oxidizing agent-cum-dopant solution of Example 3, but 3,4-ethylene The wound-type aluminum solid electrolytic capacitor of Example 35 in which dioxythiophene is used as a monomer is shown in Table 4. The breakdown voltage is 46V, the electrostatic capacity is 11.5μF, and the ESR is 34.7mΩ, while using 3,4-ethylene A mixture of ethylenedioxythiophene and propylated ethylenedioxythiophene as a monomer, the winding type aluminum solid electrolytic capacitor of Example 71 is shown in Table 9, the breakdown voltage is 55V, the electrostatic capacity is 11.8μF, and the ESR It was 31.2 mΩ, and compared with the wound aluminum solid electrolytic capacitor of Example 35, the breakdown voltage was higher, the electrostatic capacity was larger, the ESR was lower, and the capacitor properties were more excellent. the

In addition, comparing the wound-type aluminum solid electrolytic capacitor of Example 72 and the wound-type aluminum solid electrolytic capacitor of Example 36 using the same oxidizing agent and dopant solution of Example 4, 3,4-substrate A mixture of ethyldioxythiophene and propylated ethylenedioxythiophene as a monomer of the winding type aluminum solid electrolytic capacitor of Example 72, and a single use of 3,4-ethylenedioxythiophene as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 36, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

Then, the wound-type aluminum solid electrolytic capacitor of Example 73 using the same oxidizing agent-cum-dopant solution of Example 7 was compared with the wound-type aluminum solid electrolytic capacitor of Example 39, also using 3,4-substrate A mixture of ethyldioxythiophene and propylated ethylenedioxythiophene as a monomer of the winding type aluminum solid electrolytic capacitor of Example 73, and a single use of 3,4-ethylenedioxythiophene as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 39, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

[Evaluation of solid electrolytic capacitors (6)] 

In this [Evaluation of Solid Electrolytic Capacitor (6)], a mixture of 3,4-ethylenedioxythiophene and butylated ethylenedioxythiophene was used as a monomer, and the compounds of Examples 3, 4, and 7 were used. The oxidant and dopant solution were used to oxidize and polymerize it to manufacture a wound aluminum solid electrolytic capacitor, and evaluate its capacitor properties. the

Examples 74-76

First, the state of manufacturing the wound-type aluminum solid electrolytic capacitor of Example 74 using the oxidizing agent and dopant solution of Example 3 is shown below. In addition, the capacitor elements used in Examples 74 to 76 are the same as those used in Example 33, etc., and the set capacitance of the wound-type aluminum solid electrolytic capacitor is 10 μF or more, and the set ESR is 40 mΩ or less. the

That is, 80 ml of methanol was added to a mixed solution of 15 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Co., Ltd.) and 5 ml of butylated ethylenedioxythiophene synthesized in Synthesis Example 4. Immerse the capacitor element in the monomer solution, take it out and dry it at 50°C for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 3, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers and form a compound composed of 3,4 -The polymer of the mixture of ethylenedioxythiophene and butylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton, and it is externally encapsulated with an external packaging material to manufacture Example 74 Winding type aluminum solid electrolytic capacitors. the

Then, except that the oxidizing agent and dopant solution of Example 4 and Example 7 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 3, as in the case of using the oxidizing agent and dopant solution of the above-mentioned Example 3, Wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions were manufactured, and these were used as Example 75 and Example 76 wound-type aluminum solid electrolytic capacitors. the

For the wound aluminum solid electrolytic capacitors of Examples 74 to 76 manufactured as described above, ESR, electrostatic capacity, and breakdown voltage were measured in the same manner as in Example 33, and the results are shown in Table 10. the

[Table 10]

As shown in Table 10, the electrostatic capacitance of the winding type aluminum solid electrolytic capacitors of Examples 74 to 76 is 11.4 to 11.5 μF, which meets the set capacitance of 10 μF or more; the ESR is 31.9 to 32.1 mΩ, which meets the setting of 40 mΩ or less. The ESR was fixed; the breakdown voltage showed a high value of 48 to 54V, and the voltage resistance was excellent. the

Then, the wound-type aluminum solid electrolytic capacitors of Examples 74 to 76 were compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 using the same oxidizing agent and dopant solution. The wound-type aluminum solid electrolytic capacitors of Examples 74 to 76 in which a mixture of ethylenedioxythiophene and butylated ethylenedioxythiophene is used as a monomer, and 3,4-ethylenedioxythiophene alone Compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 as a single body, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

That is, both the wound type aluminum solid electrolytic capacitor of Example 74 and the wound type aluminum solid electrolytic capacitor of Example 35 used the oxidizing agent-cum-dopant solution of Example 3, but 3,4-ethylene The wound-type aluminum solid electrolytic capacitor of Example 35 in which dioxythiophene is used as a monomer is shown in Table 4. The breakdown voltage is 46V, the electrostatic capacity is 11.5μF, and the ESR is 34.7mΩ, while using 3,4-ethylene A mixture of ethylenedioxythiophene and butylated ethylenedioxythiophene as a monomer, the winding type aluminum solid electrolytic capacitor of Example 74 is shown in Table 10, the breakdown voltage is 53V, the electrostatic capacity is 11.4μF, and the ESR It was 32.1 mΩ, and compared with the wound aluminum solid electrolytic capacitor of Example 35, the breakdown voltage was higher, the electrostatic capacity was larger, the ESR was lower, and the capacitor properties were more excellent. the

In addition, comparing the wound-type aluminum solid electrolytic capacitor of Example 75 and the wound-type aluminum solid electrolytic capacitor of Example 36 using the same oxidizing agent and dopant solution of Example 4, 3,4-substrate A mixture of ethyldioxythiophene and butylated ethylenedioxythiophene as a monomer of the winding type aluminum solid electrolytic capacitor of Example 75, and a single use of 3,4-ethylenedioxythiophene as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 36, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

Then, the wound-type aluminum solid electrolytic capacitor of Example 76 using the same oxidizing agent and dopant solution of Example 7 was compared with the wound-type aluminum solid electrolytic capacitor of Example 39, also using 3,4-substrate The wound type aluminum solid electrolytic capacitor of Example 76 in which a mixture of ethyldioxythiophene and butylated ethylenedioxythiophene was used as a monomer, and 3,4-ethylenedioxythiophene alone was used as a monomer Compared with the wound aluminum solid electrolytic capacitor of Example 39, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

[Evaluation of solid electrolytic capacitors (7)]

In this [Evaluation of Solid Electrolytic Capacitor (7)], a mixture of 3,4-ethylenedioxythiophene, ethylated ethylenedioxythiophene, and propylated ethylenedioxythiophene was used as a monomer , using the oxidant and dopant solutions of Examples 3, 4, and 7 to oxidize and polymerize it to manufacture a wound aluminum solid electrolytic capacitor, and evaluate its capacitor properties. the

Examples 77-79

First, the state of manufacturing the wound aluminum solid electrolytic capacitor of Example 77 using the oxidizing agent and dopant solution of Example 3 is shown below. Note that the capacitor elements used in Examples 77 to 79 are the same as those used in Example 33, and the wound-type aluminum solid electrolytic capacitor has a set capacitance of 10 μF or more and a set ESR of 40 mΩ or less. the

That is, 10 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Corporation), 5 ml of ethylated ethylenedioxythiophene obtained in Synthesis Example 2, and 5 ml of propylated ethylenedioxythiophene synthesized in Synthesis Example 3 were mixed. 80 ml of methanol was added to the mixed solution of ethyldioxythiophene, and the capacitor element was immersed in the prepared monomer solution, taken out, and dried at 50° C. for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 3, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers and form a compound composed of 3,4 -The polymer of ethylenedioxythiophene and the mixture of ethylated ethylenedioxythiophene and propylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton, which is used The external packaging material was externally packaged to manufacture the wound aluminum solid electrolytic capacitor of Example 77. the

Then, except that the oxidizing agent and dopant solution of Example 4 and Example 7 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 3, as in the case of using the oxidizing agent and dopant solution of the above-mentioned Example 3, Wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions were manufactured, and these were used as Example 78 and Example 79 wound-type aluminum solid electrolytic capacitors. the

For the wound aluminum solid electrolytic capacitors of Examples 77 to 79 produced as described above, ESR, capacitance, and breakdown voltage were measured in the same manner as in Example 33, and the results are shown in Table 11. the

[Table 11]

As shown in Table 11, the electrostatic capacitance of the winding type aluminum solid electrolytic capacitors of Examples 77 to 79 is 11.6 μF, which satisfies the set capacitance of 10 μF or more; the ESR is 30.2 to 30.9 mΩ, which satisfies the set ESR of 40 mΩ or less ; The breakdown voltage showed a high value of 48 to 54V, and the voltage resistance was excellent. the

Then, the wound-type aluminum solid electrolytic capacitors of Examples 77 to 79 were compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 using the same oxidizing agent and dopant solution. -A mixture of ethylenedioxythiophene, ethylated ethylenedioxythiophene and propylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitors of Examples 77 to 79, and used alone Compared with the winding aluminum solid electrolytic capacitors of Examples 35, 36, and 39 in which 3,4-ethylenedioxythiophene is used as a monomer, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are better. excellent. the

That is, both the wound type aluminum solid electrolytic capacitor of Example 77 and the wound type aluminum solid electrolytic capacitor of Example 35 used the oxidizing agent-cum-dopant solution of Example 3, but 3,4-ethylene The wound-type aluminum solid electrolytic capacitor of Example 35 in which dioxythiophene is used as a monomer is shown in Table 4. The breakdown voltage is 46V, the electrostatic capacity is 11.5μF, and the ESR is 34.7mΩ, while using 3,4-ethylene The mixture of ethylenedioxythiophene, ethylated ethylenedioxythiophene and propylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitor of Example 77 is shown in Table 11, and the breakdown voltage It is 57V, the capacitance is 11.6μF, and the ESR is 30.9mΩ. Compared with the wound aluminum solid electrolytic capacitor of Example 35, the breakdown voltage is higher, the capacitance is larger, the ESR is lower, and the capacitor properties are more excellent. the

In addition, comparing the wound-type aluminum solid electrolytic capacitor of Example 78 using the same oxidizing agent-cum-dopant solution of Example 4 and the wound-type aluminum solid electrolytic capacitor of Example 36, 3,4-substrate was also used. The mixture of ethyldioxythiophene, ethylated ethylenedioxythiophene and propylated ethylenedioxythiophene as the winding type aluminum solid electrolytic capacitor of embodiment 78 of the monomer, and the single use of 3,4- Compared with the wound aluminum solid electrolytic capacitor of Example 36 in which ethylenedioxythiophene is used as a monomer, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

Then, the wound-type aluminum solid electrolytic capacitor of Example 79 using the same oxidizing agent and dopant solution of Example 7 was compared with the wound-type aluminum solid electrolytic capacitor of Example 39, also using 3,4-substrate The mixture of ethyldioxythiophene, ethylated ethylenedioxythiophene and propylated ethylenedioxythiophene is used as the winding type aluminum solid electrolytic capacitor of embodiment 79 of the monomer, and 3,4- Compared with the wound aluminum solid electrolytic capacitor of Example 39 in which ethylenedioxythiophene is used as a monomer, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

[Evaluation of solid electrolytic capacitors (8)] 

In this [Evaluation of Solid Electrolytic Capacitor (8)], a mixture of 3,4-ethylenedioxythiophene, methylated ethylenedioxythiophene, and butylated ethylenedioxythiophene was used as a monomer , using the oxidant and dopant solutions of Examples 3, 4, and 7 to oxidize and polymerize it to manufacture a wound aluminum solid electrolytic capacitor, and evaluate its capacitor properties. the

Examples 80-82

First, the state of manufacturing the wound aluminum solid electrolytic capacitor of Example 80 using the oxidizing agent and dopant solution of Example 3 is shown below. Note that the capacitor elements used in Examples 80 to 82 are the same as those used in Example 33, and the wound-type aluminum solid electrolytic capacitor has a set capacitance of 10 μF or more and a set ESR of 40 mΩ or less. the

That is, 10 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Corporation), 5 ml of methylated ethylenedioxythiophene obtained in Synthesis Example 1, and 5 ml of butylated ethylenedioxythiophene synthesized in Synthesis Example 4 were mixed. 80 ml of methanol was added to the mixed solution of ethyldioxythiophene, and the capacitor element was immersed in the prepared monomer solution, taken out, and dried at 50° C. for 10 minutes. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 3, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers and form a compound composed of 3,4 -The polymer of ethylenedioxythiophene and the mixture of methylated ethylenedioxythiophene and butylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton. The external packaging material was externally packaged to manufacture the wound type aluminum solid electrolytic capacitor of Example 80. the

Then, except that the oxidizing agent and dopant solution of Example 4 and Example 7 were used instead of the oxidizing agent and dopant solution of the above-mentioned Example 3, the situation of using the oxidizing agent and dopant solution of the above-mentioned Example 3 was the same , Wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions were manufactured, and they were used as Example 81 and Example 82 winding-type aluminum solid electrolytic capacitors. the

For the wound aluminum solid electrolytic capacitors of Examples 80 to 82 manufactured as described above, ESR, capacitance, and breakdown voltage were measured in the same manner as in Example 33, and the results are shown in Table 12. the

[Table 12]

As shown in Table 12, the electrostatic capacitance of the winding type aluminum solid electrolytic capacitors of Examples 80 to 82 is 11.3 to 11.5 μF, meeting the set capacitance of 10 μF or more; the ESR is 32.1 to 32.4 mΩ, meeting the setting of 40 mΩ or less. The ESR was fixed; the breakdown voltage showed a high value of 48 to 54V, and the voltage resistance was excellent. the

Then, the wound-type aluminum solid electrolytic capacitors of Examples 80 to 82 were compared with the wound-type aluminum solid electrolytic capacitors of Examples 35, 36, and 39 using the same oxidizing agent and dopant solution. -A mixture of ethylenedioxythiophene, methylated ethylenedioxythiophene and butylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitors of Examples 80 to 82, and used alone Compared with the winding aluminum solid electrolytic capacitors of Examples 35, 36, and 39 in which 3,4-ethylenedioxythiophene is used as a monomer, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are better. excellent. the

That is, both the wound type aluminum solid electrolytic capacitor of Example 80 and the wound type aluminum solid electrolytic capacitor of Example 35 used the oxidizing agent and dopant solution of Example 3, but 3,4-ethylene The wound-type aluminum solid electrolytic capacitor of Example 35 in which dioxythiophene is used as a monomer is shown in Table 4. The breakdown voltage is 46V, the electrostatic capacity is 11.5μF, and the ESR is 34.7mΩ, while using 3,4-ethylene A mixture of ethylenedioxythiophene, methylated ethylenedioxythiophene and butylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitor of Example 80 is shown in Table 12, and the breakdown voltage It is 54V, the capacitance is 11.4μF, and the ESR is 32.2mΩ. Compared with the wound aluminum solid electrolytic capacitor of Example 35, the breakdown voltage is higher, the capacitance is larger, the ESR is lower, and the capacitor properties are better. the

In addition, comparing the wound-type aluminum solid electrolytic capacitor of Example 81 using the same oxidizing agent-cum-dopant solution of Example 4 and the wound-type aluminum solid electrolytic capacitor of Example 36, 3,4-substrate was also used. Ethyldioxythiophene, a mixture of methylated ethylenedioxythiophene and butylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitor of Example 81, and the use of 3,4- Compared with the wound aluminum solid electrolytic capacitor of Example 36 in which ethylenedioxythiophene is used as a monomer, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

Then, the wound-type aluminum solid electrolytic capacitor of Example 82 using the same oxidizing agent and dopant solution of Example 7 was compared with the wound-type aluminum solid electrolytic capacitor of Example 39, also using 3,4-substrate Ethyldioxythiophene, a mixture of methylated ethylenedioxythiophene and butylated ethylenedioxythiophene as a monomer of the wound-type aluminum solid electrolytic capacitor of Example 82, and the use of 3,4- Compared with the wound aluminum solid electrolytic capacitor of Example 39 in which ethylenedioxythiophene is used as a monomer, the breakdown voltage is higher, the electrostatic capacity is larger, the ESR is lower, and the capacitor properties are more excellent. the

[Preparation of oxidizing agent and dopant solution (3)]

Embodiment 83～88 and comparative example 13～15

In Examples 83 to 88 and Comparative Examples 10 to 12, iron p-toluenesulfonate was used as organic iron sulfonate, and as glycidyl compound, a compound belonging to general formula (1) was used in Examples 83, 84, and 85. As the glycidyl alcohol of the monoglycidyl compound shown, in Example 86, polyethylene glycol diglycidyl ether belonging to the diglycidyl compound represented by the general formula (3) was used [Sakamoto Pharmaceutical Co., Ltd. Manufactured SR-8EGS (trade name), n in the general formula (3) is the median value of the polyethylene glycol diglycidyl ether is 8], in Example 87, using glycidyl methacrylate , In Example 88, the reactant of glycidyl methacrylate prepared in Preparation Example 1 and butanediol was used; as a polyhydric alcohol, in Examples 83-86, glycerin was used, and in Example 87, butanediol was used. Diols, oxidizer-dopant solutions were prepared as follows. Among them, the preparation of the oxidizing agent and dopant solution using iron p-toluenesulfonate as the oxidizing agent and dopant also involves the type of glycidyl compound, its addition amount, its addition ratio relative to iron p-toluenesulfonate, multiple The type of alcohol, the amount to be added, and the ratio to be added to iron p-toluenesulfonate are in the relationship shown in Table 13. In the following [Preparation method (3) of oxidizing agent and dopant solution], The type of glycidyl compound is represented by X, the amount of glycidyl compound added is represented by A (g), its ratio relative to iron p-toluenesulfonate is represented by B (%), the type of polyol is represented by Y, The amount of polyol added is represented by C (g), the ratio of its addition to iron p-toluenesulfonate is represented by D (%), and the amount of butanol added is represented by E (g). the

[The preparation method of oxidant and dopant solution (3)]

A 40% butanol solution of iron p-toluenesulfonate (the molar ratio of iron and p-toluenesulfonic acid: 1:2.74) manufactured by Teika Co., Ltd. was concentrated by distillation. The dry solids content was 67.2%. To 100 g of the above solution, Ag glycidyl compound X, Cg polyol Y, and Eg butanol were added, heated at 60°C for 1 hour, and then filtered with a glass filter GF75, and the filtrates were obtained from Examples 83 to 88 and Comparative The oxidant and dopant solutions of Examples 13-15. The calculated solid content concentration of this solution is 45.0%. In addition, in Table 13, in these oxidizing agent and dopant solutions, the addition ratio B% of glycidyl compound X to iron p-toluenesulfonate, polyol Y The addition ratio D% with respect to iron p-toluenesulfonate is also shown corresponding to each Example and a comparative example. Wherein, in this Table 13, due to the spatial relationship, glycidyl compounds and polyols are also abbreviated as follows. the

Glycidyl compounds:

EPPOL: glycidyl alcohol

PEG-DG: polyethylene glycol diglycidyl ether

Meth-G: Glycidyl Methacrylate

Preparation Example 1: Reactant of Glycidyl Methacrylate and Butylene Glycol

Polyol:

GLYOL: Glycerin

BUDOL: butanol

[Table 13]

[Evaluation of solid electrolytic capacitors (9)]

In this [Evaluation of Solid Electrolytic Capacitor (9)], 3,4-ethylenedioxythiophene was used as a monomer, and the oxidizing agent and dopant solutions of Examples 83 to 88 prepared as described above were used to produce The wound-type aluminum solid electrolytic capacitors of Examples 89 to 94 whose capacitance is set to be 10 μF or more and ESR to be 40 mΩ or less were co-doped with the oxidizing agents of Comparative Examples 13 to 15 prepared as described above. The winding-type aluminum solid electrolytic capacitors of Comparative Examples 16 to 18 manufactured from the solvent solution were compared to compare the capacitor properties, and at the same time, the evaluation of Examples 83 to 88 and Comparative Examples 13 to 18 used in the manufacture of these wound-type aluminum solid electrolytic capacitors was performed. 15 Properties of oxidant-cum-dopant solutions. the

Embodiment 89～94 and comparative example 16～18

First, the state of manufacturing the wound aluminum solid electrolytic capacitor of Example 89 using the oxidizing agent and dopant solution of Example 83 is shown below. In addition, the capacitor elements used in these Examples 89 to 94 and Comparative Examples 16 to 18 are also the same as those used in Example 33. The set capacitance of the winding type aluminum solid electrolytic capacitor is 10 μF or more, and the set ESR is 40 mΩ. the following. the

That is, the capacitor element was immersed in a monomer solution prepared by adding 80 ml of methanol to 20 ml of 3,4-ethylenedioxythiophene (manufactured by Teika Co., Ltd.), and dried at 50° C. for 10 minutes after taking it out. Afterwards, the above-mentioned capacitor element was immersed in 100ml of the oxidizing agent and dopant solution of Example 83, and after taking it out, it was heated at 70°C for 2 hours and at 180°C for 1 hour to polymerize the monomers, forming -The polymer of the mixture of ethylenedioxythiophene and methylated ethylenedioxythiophene is used as the solid electrolyte layer formed by the conductive polymer of the polymer skeleton, and it is externally encapsulated with an external packaging material to manufacture Example 89 Winding type aluminum solid electrolytic capacitors. the

Then, in addition to using the oxidizing agent and dopant solution of Examples 84-88 and Comparative Examples 13-15 to replace the oxidizing agent and dopant solution of the above-mentioned embodiment 83, and using the oxidizing agent and dopant solution of the above-mentioned embodiment 83 In the same manner as in the case of , wound-type aluminum solid electrolytic capacitors using oxidizing agent and dopant solutions were manufactured, and these were used as wound-type aluminum solid electrolytic capacitors of Examples 90 to 94 and Comparative Examples 16 to 18. the

For the wound aluminum solid electrolytic capacitors of Examples 89 to 94 and Comparative Examples 16 to 18 produced as above, ESR, capacitance, and leakage were measured to investigate whether leakage failure occurred. The results are shown in Table 14. In addition, the measurement of ESR and electrostatic capacity is to use the LCR instrument (4284A) manufactured by HEWLETT PACKARD company, under the condition of 25 ℃, measure ESR at 100kHz, measure electrostatic capacity at 120Hz. In addition, the measurement method of electric leakage and the evaluation method of occurrence of electric leakage failure are as follows. the

Leakage:

In the winding type aluminum solid electrolytic capacitor, the leakage current was measured with a digital oscilloscope after applying a rated voltage of 16 V at 25° C. for 60 seconds. the

The occurrence of poor leakage:

The electric current was measured in the same manner as in the case of measuring the above-mentioned electric leakage, and the case where the electric leakage was 100 μA or more was evaluated as occurrence of defective electric leakage. the

In addition, the measurement was performed on 50 samples of each sample, and the values of ESR and capacitance shown in Table 14 were the average value of these 50 samples and rounded off to the second decimal place. In addition, the results of research on the occurrence of leakage defects are represented by the number of all capacitors used in the test as the denominator, and the number of capacitors with leakage defects as the numerator. In this state, the "Number of leakage defects "express. the

[Table 14]

As shown in Table 14, the capacitances of the wound aluminum solid electrolytic capacitors of Examples 89 to 94 and the wound aluminum solid electrolytic capacitors of Comparative Examples 16 to 18 are all about 11 μF, satisfying the set capacitance of 10 μF In the above, the ESR is about 30mΩ, which satisfies the set ESR of 40mΩ or less. However, in the wound-type aluminum solid electrolytic capacitors of Examples 89 to 94, there is no leakage defect, or even if it occurs, the occurrence of leakage defect is small. On the other hand, in the wound-type aluminum solid electrolytic capacitors of Comparative Examples 16 to 18, a large number of leakage defects occurred. the

Industrial applicability

According to the present invention, it is possible to provide a solid electrolytic capacitor that ensures a low ESR, a large capacitance, and a high withstand voltage. In addition, according to the present invention, it is possible to provide a solid electrolytic capacitor with less occurrence of leakage defects. the

Claims (12)

1. the oxypolymerization of thiophene or derivatives thereof made the electroconductive polymer manufacturing with the oxygenant dopant solution of holding concurrently for one kind, this electroconductive polymer manufacturing is held concurrently with oxygenant, and to comprise as the electroconductive polymer manufacturing be 1 ~ 4 alcohol with the hold concurrently organic sulfonic acid iron of doping agent and carbonatoms of oxygenant to dopant solution, this organic sulfonic acid iron is tosic acid iron or methoxy benzenesulfonic acid iron, compound or its opened loop compound with glycidyl have been it is characterized in that adding, and compound or its opened loop compound with glycidyl are by the single glycidyl compound shown in the following general formula (1), diglycidyl compounds shown in the general formula (2), diglycidyl compounds shown in the general formula (3), glycerine triglycidyl group ether, two glycerine four glycidyl group ethers, methyl propenoic acid glycidyl base ester, phenylglycidyl ether, cresyl glycidyl ether, the cyclohexanedimethanol diglycidyl ether, the Resorcinol diglycidyl ether, the trimethylolpropane tris glycidyl ether, alcohol solubility Resins, epoxy, that selects in the group that alcohol soluble poly glycerine poly epihydric alcohol base ether and their opened loop compound consist of is at least a

General formula (1):

R in the formula ¹That hydroxyl, carbonatoms are that 1 ~ 5 alkyl or carbonatoms are 1 ~ 7 alkoxyl group,

General formula (2):

R in the formula ²That carbonatoms is 2 ~ 6 alkylidene group,

General formula (3):

R in the formula ³Be that carbonatoms is 2 ~ 4 alkylidene group, n is 2 ~ 20.

2. the electroconductive polymer manufacturing of putting down in writing according to claim 1 is with the oxygenant dopant solution of holding concurrently, and wherein has the addition of the compound of glycidyl or its opened loop compound with respect to organic sulfonic acid iron, is 2 ~ 40% in quality criteria.

3. the electroconductive polymer manufacturing of putting down in writing according to claim 1 is with the oxygenant dopant solution of holding concurrently, and wherein has the addition of the compound of glycidyl or its opened loop compound with respect to organic sulfonic acid iron, is 10 ~ 40% in quality criteria.

4. each electroconductive polymer manufacturing of putting down in writing is characterized in that: added polyvalent alcohol with the oxygenant dopant solution of holding concurrently according to claim 1 ~ 3.

5. the electroconductive polymer manufacturing of putting down in writing according to claim 4 is with the oxygenant dopant solution of holding concurrently, and wherein polyvalent alcohol is the polyvalent alcohol that combines 2 ~ 3 hydroxyls in carbonatoms is 2 ~ 10 aliphatic hydrocarbon.

According to claim 4 or the 5 electroconductive polymer manufacturings of putting down in writing with the oxygenant dopant solution of holding concurrently, wherein the addition of polyvalent alcohol is below 20% with respect to organic sulfonic acid iron in quality criteria.

7. electroconductive polymer is characterized in that: right to use requires 1 ~ 6 each electroconductive polymer manufacturing of putting down in writing with the oxygenant dopant solution of holding concurrently, and the oxypolymerization of thiophene or derivatives thereof is made.

8. the electroconductive polymer of putting down in writing according to claim 7, wherein the derivative of thiophene is 3,4-ethylidene dioxy thiophene.

9. the electroconductive polymer of putting down in writing according to claim 7, wherein the derivative of thiophene be 3,4-ethylidene dioxy thiophene with the group that is consisted of by the ethylidene dioxy thiophene that methylates, ethylization ethylidene dioxy thiophene, propylated ethylidene dioxy thiophene and butylation ethylidene dioxy thiophene in the mixture of at least a alkylation ethylidene dioxy thiophene selected.

10. solid electrolytic capacitor is characterized in that: right to use requires 7 ~ 9 each electroconductive polymers of putting down in writing as solid electrolyte.

11. the manufacture method of a solid electrolytic capacitor, it is characterized in that: right to use requires 1 ~ 6 each electroconductive polymer manufacturing of putting down in writing with the oxygenant dopant solution of holding concurrently, with the oxypolymerization of thiophene or derivatives thereof, make electroconductive polymer, the electroconductive polymer that use obtains is made solid electrolytic capacitor as solid electrolyte.

12. the manufacture method of the solid electrolytic capacitor of putting down in writing according to claim 11, wherein the electroconductive polymer manufacturing is when making solid electrolytic capacitor with the oxygenant dopant solution of holding concurrently, in the carbonatoms of organic sulfonic acid iron is 1 ~ 4 alcoholic solution, add compound or its opened loop compound with glycidyl, perhaps added the solution that compound with glycidyl or its opened loop compound and polyvalent alcohol form.